Inorg. Chem. 1987, 26, 2304-2306
2304
(carbamoylmethy1)thiophosphonatefragment are similar to the distances and angles found in metal-coordinated CMP ligands. The chemical and structural data presented here indicate that bifunctional (carbamoylmethy1)thiophosphonate ligands interact only weakly through their carbonyl base site with relatively hard metal centers that are important constituents in nuclear process solutions. Two important questions related to the coordination ability of these ligands remain to be addressed: How successfully will the neutral ligands complex softer metal centers present in nuclear process solutions, and can an anionic form of the ligand, [(RO)P(S)(O)CH,C(O)NR’,-], be prepared and will it provide improved coordination ability with hard metal ions? On the basis of studies of Pinkerton and c o - w ~ r k e r sit, ~might ~ be expected that an anionic thiophosphonatewould serve as an improved extractant (29) Pinkerton, A. A. Inorg. Nucl. Chem. Left. 1974, 10, 495. Pinkerton, A. A,; Schwarzenback, D. J . Chem. S o t . , Dalton Trans. 1976, 2466.
for lanthanide ions. Forthcoming communications from our laboratory will address these points. Acknowledgment. R.T.P. wishes to recognize financial support for this work from the Department of Energy, Office of Basic Energy Sciences, Contract No. MER-40079. He also wishes to recognize NSF Grants CHE-7802921 and CHE-8201374, which facilitated the purchases of the X-ray diffractometer and NMR spectrometer. Registry No. 1, 108675-65-6; 2, 108675-66-7; 3, 108675-68-9; U02(N03),(l),, 108675-67-8; (EtO),P(S)H, 999-01-9; (BuO),P(S)H, 17529-47-4; La, 7439-91-0; Nd, 7440-00-8; Er, 7440-52-0; NJ-diethylchloroacetamide, 23 15-36-8. Supplementary Material Available: Tables SI-SIV, listing hydrogen atom positional parameters, thermal parameters, and bond distances and bond angles (4 pages); Table SV, listing calculated and observed structure factors (10 pages). Ordering information is given on any current masthead page.
Contribution from the Department of Chemistry, University of Idaho, Moscow, Idaho 83843
Synthesis of Polyfluoroalkyl Esters of (Fluorosulfony1)difluoroacetic Acid and Diesters of Sulfonyldifluoroacetic Acid Ting-Ji Huang, Zhi-Xia Dong, and Jean’ne M. Shreeve* Received October 27, 1986 Several new polyfluoroalkyl(fluorosulfonyl)difluoroacetates,R@C(0)CF2S02F(Rf = CF3CH2,CF3CF2CH2,CF,CF,CF,CH,, (CF,),C(CH,), CF,CH(CH3), (CF3)2CH, CTF,&H2, CH2(CF2),CH20C(0)CF2S02F),diesters of sulfonyldifluoroacetic acid, R@C(O)CF2SO,OR; (RI = CF3CH2, (CF3)2CH; R; = CF3CH2, (CF,),CH), and alkyl (fluorosuIfonyl)difluoroacetates, RCH,(CH20C(0)CF2S02F)3.., (R = CHI, n = 0; R = 0 2 N , n = 0; R = OC(0)CF2S02F,n = 2; R = CH20C(0)CF,S02F, n = 0), resulted from the reaction of tetrafluoroethane-P-sultone with polyfluoroalkyl alcohols or polyfluoroalkoxides and alkanediols, -triols, and a -tetraol.
esters of sulfonyldifluoroacetic acid.
Introduction
Previous investigations dealing with the reactions of tetrafluoroethane-P-sultone with various nucleophilic reagents, such as amines, mercaptans, alcohols, hydrogen sulfide, and carboxylic acids gave rise to the corresponding derivatives of (fluorosulfony1)difluoroacetic CF2-CFp
I
0-so2
I
+
HE
-HF
FSO2CF2C(O)B
CF2-CFz nRtOM
I
+
0-so2
I
RtOC(O)CF2S02F
+
HF
Rf = CF3CH2, CF3CF2CH2, CF3CF2CF2CH2, C,F,,CH,; M = H; B = KF, NaF; n = 1 = CF,(CH,)CH, (CF3)2CH, (CF,),C(CH,); M = Li; n = 1 = CH2(CF2),CH2;M = H; B = KF, NaF; n = 0.5
B = e&, C6H5S,C6H5NH,C6H5(CH3)N,CH30, i-C3H70, 2Rf0L1
+
CF2-CF2
I
0-so2
O(CH2)2NCH2CH2,SCN, (C6H&N, Et2N
I
-
RfOC(O)CF2S020Rf
+
ZLIF
Rf = CF3CH2, (CF3)zCH In our continuing efforts toward the syntheses of precursors to new highly conducting, hydrolytically and thermally stable polyfluorinated sulfonic acids, we have taken advantage of the electrophilic sulfur center in sultones to prepare a variety of mono-, di-, tri-, and tetrasulfonyl fluorides. Tetrafluoroethane-P-sultone was reacted with polyfluoroalkyl alcohols to yield new polyfluoroalkyl (fluorosulfonyl)difluoroacetates,and di(polyfluoroalky1) ( 1 ) England, D. C.; Dietrich, M. A,; Lindsey, R. V., Jr. J . Am. Chem. SOC. 1960, 82, 6181. (2) Knunyants, I. L.; Sokol’ski, G.A . Angew. Chem. 1972, 84, 623. (3) Canich, J. M.; Ludvig. M. M.; Gard, G. L.; Shreeve, J. M. Inorg. Chem. 1984, 23, 4403. (4) Sokol’ski,G. A,; et al. Izu. Akad. Nauk SSSR, Ser. Khim. 1967, 1524. ( 5 ) Sokol’ski, G. A.; et al. Izu. Akad. NaukSSSR, Ser. Khim. 1965, 1613.
0020-1669/87/1326-2304$01.50/0
In addition, alkyl poly[(fluorosulfonyl)difluoroacetates] were synthesized. RCHn(CH20H)3-,
+
CFz-CF2 (3-n)I
0-so2
I
RCHn(CH20C(O)CF2 SO2F)g-n
R = CH3, n = 0; R = 0 2 N , n = 0; R = OC(0)CF2S02F,n = 2; R = CH20C(0)CF2S02F,n = 0 Results and Discussion Polyfluoroalkyl (fluorosulfony1)difluoroacetates were synthesized in good Yields by the reaction between tetrafluoroethane-P-sultone and polyfluoroalkoxides or polyfluoroalkyl al0 1987 American Chemical Society
Inorganic Chemistry, Vol. 26, No. 14, 1987 2305
Synthesis of Polyfluoroalkyl Esters cohols (1:l) in the presence of NaF or KF at room temperature. On treatment of tetrafluoro-(3-sultone with a 2:l excess of the polyfluoroalkoxide, diesters, RQC(0)CF2S020Rf,were formed. The following mechanism describes the formation of the ester or diester:
or
RfO-
+
C F2- CF2
I
I
V-"
-
(in -
RtOS02CF2C-0-
(9 -OR1
RfOC(O)CF2 SOPOR(
These routes to the stable products are strongly supported by the following isomerization of p-sultones to their acyclic isomers: XCF-CF2
I
I
02s-0 E t s N or H*d< X
I
dloxane4 >-Or
* F . SFs
FC(O)CMSO2F
Ethyl (fluorosu1fonyl)difluoroacetate when reacted with sodium ethoxide gave sodium (ethoxycarbonyl)difluoromethanesulfonate.6 It is likely that C2HSOC(0)CF2S020C2H5 was formed in the first stage of the reaction, and it then alkylates the sodium salt. The overall reaction is described by C2HSOC(O)CF2SO2F C2H50Na [C2HSOC(0)CF2S020C2Hs NaF] C2HSOC(O)CF2SO20Na C2HSF
+
-+ +
In contrast when (CF3)2CHOC(0)CF2S02F was reacted with lithium 2,2,2-trifluoroethoxide,(CF3)2CHOC(0)CF2S020CH2CF3 was obtained due to the inductive effect of the polyfluorinated ethyl substituent, Le.
-
(CF3),CHOC(0)CF2S02F+ CF,CH20Li (CF,),CHOC(O)CF2S020CH2CF3 The new mono- and diesters described in this work are all colorless, slightly volatile or involatile liquids at 25 OC. They are stable toward water. The carbonyl stretching vibrations for these esters fall typically in the 1780-1820-cm-' region. The 19FNMR resonance for the fluorosulfonyl group is found invariably in the range C#J 42.00 0.75 as a triplet. The conversion of these materials to ethers and finally to their sulfonic acid derivatives will be reported in due course.
*
Experimental Section Materials. Tetrafluoroethane-@-sultonewas prepared according to the literature.' The other materials were obtained as follows: (CF,),CHOH, CF,CH(CH,)OH, CH3C(CF3)20H3CF$F$F2CH20H, C,F,,CH,OH, and HOCH,(CF,),CH,OH from PCR; CF3CF2CH20Hfrom Fairfield; CF3CH,0H, C(CH,OH),, CH3C(CH20H),, HOCH2CH,0H, and O,NC(CH,OH), from Aldrich. They were used as received. (6) Dmitriev, M. A.; Sokol'ski, G. A.; Knunyants, I. L. Izu. Akad. Nauk SSSR, Ser. Khim. 1960, 1227.
General Procedures. A conventional Pyrex glass vacuum line equipped with Heise Bourdon tube and Televac pressure gauges was used to manipulate the volatile starting materials and to free products from impurities. On occasion, products were purified by using bulb-to-bulb distillation. Volatile compounds were measured quantitatively by using PVT techniques. Infrared spectra were recorded with a Perkin-Elmer 599 spectrometer as liquid films between KBr disks. I9F NMR spectra were obtained on a JEOL FX-90Q Fourier transform spectrometer operating at 84.26 MHz. CDCI, was used as the solvent with CFCI, as an external reference. Chemical shifts upfield from CFCI, were assigned negative values. lH NMR spectra were obtained at an operating frequency of 89.94 MHz. Mass spectra were recorded with a VG 7070 HS mass spectrometer with an ionization potential of 17 or 70 eV. Elemental analyses were performed by Beller Mikroanalytisches Laboratorium, Gottingen, West Germany. Preparation of CF3CH20C(0)CF2S02F. 2,2,2-TrifluoroethanoI (2 mmol) was condensed into a Pyrex reaction flask charged with tetrafluoroethane-@-sultone(2.5 mmol) and sodium fluoride (3 mmol) at -196 OC; the mixture was warmed very slowly to 25 OC,and stirred for 24 h. The reaction mixture was distilled by using trap-to-trap techniques. Unreacted FC(0)CF2S02F was held in the trap at -196 OC. The product and traces of CF,CH,OH were retained in a trap at -40 OC. A 90% yield of the pure, colorless liquid CF3CH20C(0)CF2S02Fwas obtained by passing the material over P4010.The infrared spectrum of CF,CH,OC(O)CF,SO,F has bands as follows: 2982 w, 1808 s, 1500 w, 1465 s, 1410 m, 1320 s, 1276 s, 1240 s, 1190 s, 1150 s, 1075 w, 1043 m, 970 m, 830 s, 806 s, 725 w, 650 m, 590 w, 560 w cm-'. The ' H NMR spectrum consists of a quartet at d 4.72 (JCH2
